Organic peroxides, their preparation, and their applications

ABSTRACT

Tetraperoxides of the formula   where X is a bivalent radical such as alkylene; R1 is hydrogen or an organic radical; R2 is alkylene alkoxy carbonyl; and R3 is an organic radical. Method of preparing tetraperoxides by addition reaction between a bis-hydroperoxide and a carbonyl compound to form a dihydroxy diperoxide, followed by condensation of the dihydroxy diperoxide with a tertiary monohydroxide. The tetraperoxides are useful for vulcanizing saturated elastomers, crosslinking plastomers, and initiating radical polymerization.

Sacrini et a].

[ ORGANIC PEROXIDES, THEIR PREPARATION, AND THEIR APPLICATIONS [75]Inventors: Egeo Sacrini; Claudio Cavallotti,

both of Milan, Italy '[73] Assignee: The B.F. Goodrich Company,

Akron, Ohio [22] Filed: Apr. 23, 1975 [21] Appl. No.: 570,601

Related US. Application Data [62] Division of Ser. No. 373,934, June 27,1973, which is a division of Ser. No. 62,128, Aug. 7, 1970, Pat. No.3,775,465.

[30] Foreign Application Priority Data Aug. 12, 1969 Italy 20839/69 [52]US. Cl 260/610 R [51] Int. Cl. C07C 179/06 [58] Field of Search 260/610R, 610 A [56] References Cited UNITED STATES PATENTS 3,402,205 9/1968Gregory 260/610 R Dec. 23, 1975 3,419,577 12/1968 Breckert et a1.260/610 R Primary Examiner-James 0. Thomas, Jr.

Assistant ExaminerW. B. Lone Attorney, Agent, or Firm-Hubbell, Cohen, &Stiefel [57] ABSTRACT Tetraperoxides of the formula where X is abivalent radical such as alkylene; R is hydrogen or an organic radical;R is alkylene alkoxy carbonyl; and R is an organic radical. Method ofpreparing tetraperoxides by addition reaction between abis-hydroperoxide and a carbonyl compound to form a dihydroxydiperoxide, followed by condensation of the dihydroxy diperoxide with atertiary monohydroxide. The tetraperoxides are useful for vulcanizingsaturated elastomers, crosslinking plastomers, and initiating radicalpolymerization.

1 Claim, No Drawings ORGANIC PEROXIDES, THEIR PREPARATION,

AND THEIR APPLICATIONS This is a division of application Ser. No.373,934, filed June 27, 1973, which is in turn a division of applicationSer. No. 62,128, filed Aug. 7, 1970, now US. Pat. No. 3,775,465.

BACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates to a new series of or- THE INVENTION The presentinvention provides a particular type of new organic peroxides havinggood stability and low volatility at temperatures higher than roomtemperature, such peroxides being particularly suitable both asvulcanizers for elastomers and as crosslinking agents for plastomers.

The present invention provides a new series of organic peroxidescharacterized by the presence of four peroxidic groups, these peroxidesbeing defined by the general formula:

wherein:

each of R may be hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl,alkylcycloalkyl, said groups having l-IC, aryl,'haloaryl, alkaryl, saidgroups having 6l5 C, oxyalkyl, oxyalkylaryl, or oxycy cloalkyl, saidgroups having 'l-15 C, each of R may be alkylene alkoxy carbonyl whereinalkylene group has 1-4 C and alkoxygroup has 1 to 4 C'such as methyleneethoxy carbonyl,

or the like;

each of R may be alkyl, haloalkyl, said groups having 4-12 C,cycloalkyl, halocycloalkyl, alkylcycloalkyl, said groups having 4-21 C,aryl, alkaryl, haloaryl, said groups having 6-24 C oxyalkyl,oxyalkylaryl,

oxycycloalkyl, said groups'having4-24 C, or acyl,

having 6-12 C; preferred radicals being tertiary alkyl such astert.-butyl, tert.-amyl, and cumyl; and

2 haloalkinylene, aryl alkinylene, said groups having 2-'-l8'C, oxyalkylene, having 212 C, arylene, alkyl arylene, or halo arylene, said groupshaving 6-18 C. Examples of compounds within the above cited generalformula include:

I) 01-01 [2-t'ert.-butyl peroxy-(3-ethoxycarbonyl)-isopropylidene-2peroxy] 1,3 diisopropylbenzene,

2) 01-01 [2-terti-butyl peroxy-(3-ethoxycarbonyl) isopropylidene-2peroxy] 1,4 diisopropylbenzene,

3) a-d' [2-cumyl peroxy-(3-ethoxycarbonyl)-isopropylidene-2'peroxy] 1,3diisopropylbenzene,

4) 04-01 [2- cumyl peroxy-( 3-ethoxycarbonyl)-iso- 'propylidene-Zperoxy] 1,4 diisopropylbenzene.

The peroxides of this invention show the unusual properties of beingendowed with a good stability and a low volatility at temperatureshigher than room temperature. These properties permit the compounds tobe readily incorporated both into the plastomers as crosslinking agents,and into elastomers as vulcanizing agents, without giving rise totroublesome secondary phenomena.

This invention provides, moreover, a process for the preparation of theforegoing peroxides as well as of other known tetraperoxides, e.g.,those disclosed in US. Pat. No. 3,489,730 at column 1, lines 4l-59, thecontents of which are incorporated herein by reference, through twosuccessive steps. In the first step there occurs an addition reactionbetween a bishydroperoxide and a carbonyl compound, withthe formation ofa diperoxide having a double hydroxy function, In the second step thereoccurs a condensation reaction between the previously obtaineddiperoxide and a mono-hydroxide of the tertiary type.

According to a preferred embodiment, the desired tetraperoxides areprepared in the presence of a suitable solvent by reacting in the firststep I) an organic carbonyl compound of the formula: R CO-R wherein eachof R and R -may be hydrogen, alkyl,

X is alkylene,*haloalkylene, arylalkylene, said groups having 2l8 C,alkenylene, halo-alkenylene, arylalkenylene, said groups'ha'ving 21 8 C,alkinylene,

haloalkyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl,

said groups having l-l5 C, aryl radicals, haloaryl, alkaryl, said groupshaving ,6- l5 C, oxyalkyl-, oxyalkylaryl-,

Y oxycycloalkyl, said groups having ;ll5 C; R may also be an alkylenealkoxy carbonylwherein alkylene has 1 to 4C and alcoxy has 1 to 4 C; orR and R together with the central carbon atom form a cycloaliphaticring, having 4 l6 C, which ring may be alkyl-, halogenorhydroxysubstituted, having 1-8 C, with (2) a bis-hydroperoxide of theformula: HOO-X-OOI-l, in which X has the previously defined meaning, thereaction being carried out in the presence of a suitable dehydratingagent and an acid catalyst, at a temperature of from about 30 to +C,preferably from about --10C to +50C. v

The compound thus obtained is a diperoxide of the formula: v

wherein i R, and R and" X have the previously defined meanmgs.

Examples of compounds embraced by the above formula include:

a) a-a(2-hydroxy-isopropylidene-2-peroxy) 1,3 diisopropylbenzene;

b) a-a' (2-hydroxy-isopropylidene-2-peroxy) 1,4 diisopropylbenzene: A

c) a-a (2-hydroxy-2-phenylethyl-2-idene-peroxy) 1,3

diisopropylbenzene;

d) war [2-hydroxy-(3-ethoxycarbonyl)-isopropylidene-Z-peroxy] 1,3diisopropylbenzene;

e) H1 [2-hydroxy-(3-ethoxycarbonyl)-isopropylidene-Z-peroxy] 1,4diisopropylbenzene;

f) ma 1-hydroxy-cyclopentylidenel-peroxy) 1,3

diisopropylbenzene;

g) a-a' l-hydroxy-cyclopentylidene- 1 -peroxy) 1,4

diisopropylbenzene;

h) a-a l-hydroxy-cyclohexylidene- 1 -peroxy) 1,3

diisopropylbenzene; 1

i) a-a l-hydroxy-cyclohexylidenel -peroxy) 1,4

The peroxides defined by the foregoing formula are new compounds, andare useful as initiators of radical polymerizations.

The diperoxides obtained as described above are then reacted in thesecond step of the process, with mono-hydroperoxides in the presence ofsuitable dehydrating agents and catalysts of an acid nature at atemperature between about -30 and +80C, preferably between about and+50C.

Examples of bis-hydroperoxides which are suitable for use in the firststep of the process, include: diisopropylbenzene-l ,3-dihydroperoxide;diisopropylbenzene- 1,4-dihydroperoxide;2,5-dimethyl-2,5-dihydroperoxy-.

hexane; 2,5-dimethyl-2,5-dihydroperoxide-hexene-3;2,5-dimethyl-2,5-dihydroperoxy-hexyne-3; etc.

Examples of carbonyl compounds suitable for use in the first step of theprocess include: aliphatic ketones such as methyl ethyl ketone, acetone;substituted aliphatic ketones such as ethyl-acetacetate; cyclo-ketonessuch as cyclopentanone, cyclohexanone and cyclododecanone;cyclo-alkyl-ketones such as 4-terbutyl cyclohexanone; alkylarylaldehydessuch as cinnamaldehyde; alkylheterocyclic aldehydes such as furylacrylic aldehyde.

The mono-hydroperoxides which may be used in the second step of theprocess are of the type: R, OOH wherein R has the above defined meaning,preferably wherein a tertiary carbon atom is bound to the hydroperoxidegroup. Examples of such mono-hydroperoxides include: tert.-butylhydroperoxide and substituted tert.-butyl hydroperoxides, cumylhydroperoxide and substituted cumyl hydroperoxides, methyl-cyclohexyl 4hydroperoxide, 2-methyl-2 hydroperoxide-butyn-3, menthane hydroperoxide,etc.

Solvents suitable for use in this invention include linear aliphatichydrocarbons having 6-10 C; linear aliphatic halogenated hydrocarbonshaving 1 or 2 C and 1 'to 4 Cl; cycloaliphatic hydrocarbons having 6-10C; aromatic hydrocarbons having 6-9 C, which may be halogenated with 1or 2 Cl; ethers for instance, ethyl ether.

The molar ratio between the bis-hydroperoxide and the carbonyl compoundused in the addition reaction should be between 1:1.2 and 1:10, andpreferably between 1:1.5 and 1:5. Catalysts of an acid nature may be ofthe HCl, H280 and HClO type.

For the second step of the process, wherein a condensation reactiontakes place, the molar ratio of diperoxide having a double hydroxyfunction to monohydroperoxide should be between 1:2 and 1:10, andpreferably between 1:3 and 1:5.

As previously noted, the overall process of this invention can beemployed to prepare a wide variety of tetraperoxides, many of which areknown, many of which are new. Examples of tetraperoxides which can bemade by the process of this invention include the following:

1) a-a (2-cumyl peroxy-isopropylidene-2-peroxy) 1,3

diisopropylbenzene; 1 2) 01-11 (2-cumyl peroxy-isopropylidene-2-peroxy)1,4

diisopropylbenzene; 3) a-a (2-tert.-butyl-peroxy-2-phenylethyl-2-idene-2- peroxy) 1,3 diisopropylbenzene; 4) a-a(2-tert.-butyl-peroxy-2-phenyl ethyl-2-idene-2- peroxy) 1,4diisopropylbenzene; 5)- oz-a (2-cumyl peroxy-2-phenyl ethyl-2-idene-2-peroxy) 1,3 diisopropylbenzene; 6) 01-11 (2-cumyl peroxy-2-phenylethyl-2-idene-2- peroxy) 1,4 diisopropylbenzene; 7) a-a' [2-tert.-butylperoxy(3-ethoxycarbonyl) isopropylidene-2-peroxy] 1,3diisopropylbenzene; 8) 01-02 [2-tert.-butyl peroxy-(3-ethoxycarbonyl)isopropylidene-2-peroxy] 1,4 diisopropylbenzene; 9) 01-01 [2-cumylperoxy-(3-ethoxycarbonyl)-isopropylidene-Z-peroxy] 1,3diisopropylbenzene; 10) 01-01 [2-cumyl propylidene-2peroxy] 1,4diisopropylbenzene; 11) 01-01 (1-tert.-butyl peroxy cyclopentylidene-1-peroxy) 1,3 diisopropylbenzene; 1,2) a-af (1-tert.-butylperoxy-cyclopentylidene-1- peroxy) 1,4 diisopropylbenzene; 13) 01-01(l-cumyl peroxy-cyclopentyliden e-l-peroxy) 1,3 diisopropylbenzene; 14)ma (l-cumyl peroxy-cyclopentylidene-l-peroxy) 1,4 diisopropylbenzene;15) 01-01 (1-tert.-butyl peroxy-cyclohexylidene-lperoxy) 1,3diisopropylbenzene; l6) a-a' (l-tert.-butylperoxy-cyclohexylidene-lperoxy) 1,4 diisopropylbenzene; v 17) 05a(l-cumyl peroxy-cyclohexylidene-l-peroxy) 1,3 diisopropylbenzene; 18)01-01 (l-cumyl peroxy-cyclohexylidene-l-peroxy) 1,4 diisopropylbenzene;19) 11-01 l-tert.-b uty1 peroxy-4 tert.-butyl-cyclohexylidene-l-peroxy)1,3 diisopropylbenzene; 20) 01-01 l-tert.-butyl peroxy-4tert.-butyl-cyclohexylidene-l-peroxy) 1,4 diisopropylbenzene; 21) a-a(1tert.-butyl peroxy cyclododecylidene-lperoxy) 1,3 diisopropylbenzene;

peroxy( 3-ethoxycarbonyl )-isodenel -peroxy] l ,3 diisopropylbenzene.

Both the hydroxyl diperoxides and the tetraperoxides obtained accordingto this invention are soluble in aliphatic and aromatic hydrocarbons,chlorinated aliphatic and aromatic solvents, aliphatic alcohols, andaliphatic esters.

According to another and particularly interesting aspect of thisinvention, it has been found that the peroxides of this invention act asexcellent vulcanizing agents for saturated elastomers, crosslinkingagents for plastomers, and as initiators for radical polymerizations.

vulcanization of the ethylene-propylene copolymer is carried out at atemperature comprised between about 140 and 190C, preferablyv betweenabout 150 and 180C, for periods of from about to 200 minutes, preferablybetween about 5 and minutes.

The concentration by weight of the peroxide should be between about 0.5and 10 percent, preferably between about 2 and 5 percent, based on theelastomer.

A particularly suitable vulcanization recipe is the following:

ethylene/propylene copolymer 100 parts carbon black -80 parts ZnO l-lOparts sulfur (HS-0.5 parts peroxide 0.0050.()2 parts The use of theperoxides of the invention as crosslinking agents for plastomers findsspecific application for polyolefins, particularly polyethylene,inasmuch as its mechanical resistance at high temperatures is improved,its brittleness at low temperatures is decreased, and its solubility toaliphatic hydrocarbons, aromatic hydrocarbons, and chlorinatedhydrocarbons is decreased. Moreover, the resistance of the polymer tolight, to weather and to aging is improved.

The crosslinking is carried out at a temperature comprised between about100 and 200C, preferably between about 145 and 165C, at a pressurebetween about 50-200 kg/cm for a period of time of from about 5 to 60minutes, preferably from about 10 to minutes.

The concentration by weight of the peroxide is between about 0.5 and 10percent, preferably between about 2 and 5 percent, based on theplastomer.

The most significant advantages offered by the use of the peroxidesaccording to this invention in the vulcanization of saturated elastomersand in the crosslinking of plastomers, are:

1. The capability of obtaining virtually odorless vulcanized andcrosslinked products;

2. Absence of blooming phenomena;

3. Short vulcanization times and low vulcanization temperatures;

4. Improved effectiveness remains unchanged even in the presence ofconventional additives such as 6 fillers, reinforcing agents, additives,co-agents, plasticizers, pigments and anti-oxidants. The followingexamples further illustrate the invention. All parts are by weightunless otherwise stated.

EXAMPLE-1 200 cc of ethyl ether,60.6 g of1.3-diisopropy1benzene-bis-hydroperoxide-sodium salt at 67 percent, 51 gof cyclopentanone' at 99%1and 20 g of ground anhydrous calcium chloride,were introduced into a flask provided with a stirrer.

This mixture was cooled down to from 15 10C and over-a20 minute periodthere were slowly introduced 60 g of HCl at 36 percent. The mixture wasthen stirred for 1 hour at 5C. The ether solution was then washed withwater and treated with anhydrous sodium sulfate.

The a-a( l-hydroxy-cyclo pentylidene- 1 -peroxy) 1 3 diisopropylbenzenethus obtained (53 g determined analytically) showed the followingcharacteristics:

98% 30 minutes at 98C 45C lodometric titre Half life Decompositiontemperature C found 66.40 (calculated 66.98) H found 8.2 (calculated8.69)

EXAMPLE 2 53 g of a-a'(1-hydroxy-cyclopentylidene-l-peroxy) 1 ,3diisopropylbenzene obtained according to Example 1 and dissolved in 200cc of ethyl ether, 44 g of tert. butyl hydroperoxide at and 40 g ofground anhydrous calcium chloride, were introduced into a flask providedwith a stirrer.

The ether solution was then cooled down to 10C and over a 5 minuteperiod there were introduced 20 g of hydrochloric acid at 36 percent.The temperature was permitted to rise to 0C and the solution was stirredfor 1 hour at 0C.

The ether phase was then washed, first with water, then with NaOH at 5percent, and then again with water. The solvent was then removed undervacuum at 30C, therebyobtaining 69 g of product, namely, aa'(l-tert-butyl peroxy-cyclopentylidene l -peroxy) 1 ,3 diisopropylbenzene.

The product thus obtained showed the followin characteristics:

0.945 n,, l .447 lodometric titre: I 99% Decomposition temperature: 114C Half life at 123C: 30 minutes C7zz found 66.5 (calculated 66.88)11%: found 9.4 (calculated 9.36)

EXAMPLE 3 300 cc of ethyl ether, 41.8 g of 1,4-diisopropylbenzenebis-hydroperoxide at 97.3%, 37.8 g of 4-tertbutyl-cyclohexanone at 98percent, and 18 g of ground anhydrous calcium chloride were introducedinto a flask provided with a stirrer.

The mixture was then cooled down to 0C and over a 5 minute period therewere introduced 24 g of HCl at 7 36 percent. The temperature wasmaintained at C and the mixture was kept under stirring for 1 hour.

The ether solution was then washed with water and then concentratedunder vacuum, avoiding completely evaporation of the ether.

The a-a( 1hydroxy-4-tert.butyl-cyclohexylidene-1peroxy)1,4-diisopropylbenzene thus obtained (66 g determinedanalytically) was kept in solution so as to be ready for subsequentreaction, and showed the following characteristics:

lodometric titre 98.59? Decomposition temperature 62C Half-life at 1 12C30 minutes C 7a: found 70.4 (calculated 71.87) H "/0: found 10.1(calculated 10.18)

EXAMPLE 4 150 g of ether solution containing 66 g of a-a'( 1-hydroxy-4-tert.butyl-cyclohexylidene-l-peroxy)1,4- diisopropylbenzeneobtained according to Example 3, 44g of tert. butyl hydroperoxide at 80percent, and 42 g of ground anhydrous calcium chloride were introducedinto a flask provided with a stirrer.

The solution was then cooled down to 5C and over a 5 minute period therewere introduced 30 g of HO at 36 percent. Care being taken not to exceed0C, the solution was then left under stirring at this temperature for 1hour. The ether phase was washed with water, then with NaOH at 5percent, and'then again with water.

The solvent was subsequently removed under vacuum at 30C, therebyobtaining a residue (76 g) identified as a-a'(ltert.butyl-peroxy-4-tert.butylcyc1ohexylidenel peroxy) l ,4diisopropylbenzene and having the following characteristics:

Melting point 3234C lodometric titre 99.8% Decomposition temperature109C Half life at 121C 30 minutes C found 69.6 (calculated 70.75) H "/0:found 10.5 (calculated 10.40)

EXAMPLE 5 200 cc of benzene, 81 g of1,3-diisopropylbenzenebis-hydroperoxide-sodium salt at 67 percent, 33.5g of cyclohexanone at 99 percent, and 25 g of ground anhydrous calciumchloride were introduced into a flask provided with a stirrer.

The mixture was then cooled down to l0C and over a period of 30 minutesthere were slowly intro duced 80 g of HCl at 36 percent. The mixture wasthen left under stirring for 1 hour at -5C.

The benzene solution was then washed with water and thereafter wasdehydrated with anhydrous sodium sulfate.

The a-a( 1hydroxy-cyclohexylidene- 1 peroxy) 1 ,3- diisopropylbenzenethus obtained (71 g determined analytically) was maintained in solution.This product showed the following characteristics:

lodometric titre: 98% Decomposition temperature: 55C Half-life at 1 C 30minutes C 7!: found 68.0 (calculated 68.22) H "/1: found 9.0 (calculated9.07)

EXAMPLE 6 Into a flask fitted with a stirrer were introduced 71 g ofoz-a( lhydroxy-cyclohexylidene-1peroxy) l ,3- diisopropylbenzenedissolved in 200 cc of benzene (obtained according to Example 5), 5 8 gof tert.-buty1 hydroperoxide at 80 percent, and 45 g of ground anhydrouscalcium chloride.

' The benzene solution was cooled down to l0C and over a 5 minute periodthere were introduced 27 g of hydrochloric acid at 36 percent. Thesolution was then left under stirring for 1 hour at 5/0C. The organicphase was then washed, first with water, then with NaOH at 5 percent,and then again with water.

The benzene solution was then filtered on a layer of anhydrous sodiumsulphate and celite and the solvent was removed under vacuum at 30C.

Thereby were obtained 91 g of a product identified as oz-a'(1-tert.-butyl-peroxy-cyclohexylidenel peroxy)1,3-diisopropylbenzene. Theproduct showed the following characteristics:

C found 67.5 (calculated 67.81) H 7:: found 9.6 (calculated 9.6

EXAMPLE 7 lnto a flask provided with a stirrer were introduced 200 cc ofbenzene, 50 g of 1,3diisopropylbenzene-bishydroperoxide (sodium salt) at60 percent, 15.8 g of methylethylketone, and 30 g of ground anhydrouscalcium chloride. The mixture was cooled down to 5 to 0C and over a 30minute period there were then slowly introduced 49 g of HCl at 36%. Themixture was then stirred for 1 hour at 0C. The benzene solution waswashed with water and then dehydrated with anhydrous sodium sulfate.

The a-a(2-hydroxy-n-butyliden-2 peroxy) l ,3-diisopropylbenzene thusobtained (37 g determined analytically) showed the followingcharacteristics:

97% 50C 30 minutes EXAMPLE 8 Into a flask provided with a stirrer wereintroduced 37 g of a-a(2-hydroxy-n-butyliden-Z-peroxy)1,3-diisopropylbenzene (obtained according to Example 7), dissolved in 200cc of benzene, 40 g of tert.-butyl hydroperoxide at percent, and 40 g ofground calcium chloride. The benzene solution was then cooled down to 5Cand over a 10 minute period there were introduced 30 g of hydrochloricacid at 36 percent. The temperature was allowed to rise to +5C and thesolution was stirred for 1 hour at this temperature. The benzene phasewas then washed with water, then with NaOH at 5 percent, and again withwater.

The solvent was then removed under vacuum at 30C, thereby obtaining 39.5g of a slightly straw-colored liquid residue identified as a-a(2tert.-butyl- 9 peroxy-n-butyliden-2 peroxy) 1,3-diisopropylbenzene. Thisproduct showed the following Characteristics:

C found 65.8 (calculated 65.34) H found 9.7 (calculated 9.7)

EXAMPLE 9 Into a flask provided with a stirrer were introduced 100 cc ofbenzene, 100 g of 1,3-diisopropylbenzenebis-hydroperoxide (sodium salt)at 60 percent, 81 g of 2,6,8-trimethyl-4-nonanone and 30 g of groundanhydrous calcium chloride. The mixture was then cooled down to 5C to C,and over a 30 minute period there were introduced 95 g of hydrochloricacid at 36 percent. The temperature rose to +C and the mixture was thenleft under stirring for 1 hour. The benzene phase was then washed withwater and then treated with anhydrous sodium sulfate.

The a-a'(4-hydroxy-2,6,8 trimethyl-nonylidene-4- peroxy)1,3-diisoprophylbenzene thus obtained (115 g determined analytically)showed the following characteristics:

lodometric titre: 94% 3O Decomposition temperature: 67C Half-life at107C minutes C 701 found 71.7 (calculated 72.68) H found 10.9(calculated 11.18)

EXAMPLE l0 1 15 g of 01-01 (4-hydroxy-2,6,8-trimethyl-nonylidene- 4peroxy)1,3-diisopropylbenzene (obtained according to Example 9)dissolved in 100 cc of benzene, 79.5 g of tert. butyl hydroperoxide at75 percent, and g of ground anhydrous calcium chloride were introducedinto a flask provided with a stirrer.

The solution was then cooled down to 5C and over a 10 minute periodthere were introduced 40 g of hydrochloric acid at 36 percent. Due tothe exotherm, the temperature rose to +5C and the solution was then leftunder stirring at +5C for 1 hour.

The benzene phase was washed with water, then with NaOH at 5 percent,and again with water. The solvent was then removed under vacuum at 30C,thereby obtaining a liquid residue of a slight brownish color which wasidentified as a-a(4-tert.-butyl-peroxy-2,6,8-trimethyl-nonylidene-4-peroxy) l ,3-diisopropylbenzene, which producthad the following characteristics:

lodometric titre:

Decomposition temperature: Half-life at 116C C 70: found 71.3(calculated 71.50) H 7:: found 11.] (calculated 11.18)

92% 109C 30 minutes EXAMPLE 1 1 10 The mixture was then cooled down to10C and over a 25 minute period there were introduced 60 g ofhydrochloric acid at 36 percent. The mixture was stirred for 1 hour at+5C. The benzene solution was then washed with water and thereafter wasdehydrated with anhydrous sodium sulfate. 1

The a-a( lhydroxy-cyclododecylidene-l peroxy)1,4-diisopropylbenzene thusobtained g determined analytically) showed the followingcharacteristics:

lodometric titre: 98% Decomposition temperature: 59C Half-life at 1 14C:30 minutes C 72': found 73.3 (calculated 73.17 H found 10.3 (calculated10.58)

EXAMPLE l2 Into a flask provided with a stirrer were introduced 80 g ofa-oz(lhydroxy-cyclododecylidene-l peroxy) 1,4-diisopropylbenzene(obtained according to Example l 1) dissolved in 300 cc of benzene, 66.7g of tert.- butyl-hydroperoxide at 66.7 percent, and 40 g of groundanhydrous calcium chloride. The benzene solution was then cooled down to0C and over a 10 minute period there were introduced 5 g of hydrochloricacid at 36 percent.

The temperature was then allowed to rise to +5C and the solution wasthen stirred for 1 hour at this temperature (+5C). The benzene phase wasthen washed with water, with NaOH at 5 percent, and then again withwater. I

The solvent was then removed under vacuum at 40C, thereby obtaining 48 gof a yellow liquid residue lodometric titre: 9971 Decompositiontemperature: 109C Half-life at C: 30 minutes C found 0.2 (calculated71.89) H found 10.9 (calculated 10.7)

EXAMPLE 13 Into a flask provided with a stirrer, were introduced 50 ccof benzene, 50 cc of ethyl ether, 60.6 g of 1.3-diisopropyl-benzenebis-hydroiaeroxide (sodium salt) at 67 percent, 27.7g of benzyl-methylketone at 97 percent, and 30 g of ground anhydrouscalcium chloride. This mixture was then cooled down to l5C and then wereslowly added, over a 30 minute period, 60 g of HCl at 36 percent.Thereafter the mixture was kept under stirring for 1 hour at 5C.

The organic solution thus obtained was then washed with water and thenwas dehydrated with anhydrous sodium sulfate. The product thus obtained(37 g determined analytically), identified as a-a'[2-hydroxy-(3- phenyl)propylidene-Z peroxy] 1,3-diisopropylbenzene, was kept in solution.

An isolated analytical sample showed the following characteristics:

lodometric titration: Decomposition temperature: 70C Half-life at 104C:30 minutes c found 71.9% (calculated 72.85) H found 7.4% (calculated7.74)

EXAMPLE 14 Into a flask provided with a stirrer were introduced 37 g ofa-a[2-hydroxy-(3-phenyl)propylidene-2 peroxy] 1,3 diisopropylbenzene(obtained according to Example 13) dissolved in 50 cc of benzene and 50cc of ether, 45.2 g of tert.-butyl hydroperoxide at 80 percent, and 20 gground anhydrous calcium chloride. This solution was then cooled down toC and in over a minute period there were added 20 g of hydrochloric acidat 36 percent.

The exotherm caused the temperature to rise to +5C and the solution wasmaintained at this temperature for one hour under stirring. Thereafterthe organic phase was washed with water, with NaOH at 5 percent, andagain with water until neutrality.

Then the solvent was removed under vacuum at 50C, thereby obtaining aslightly opalescent liquid residue (44 g), identified asa-a[2-tert.-butyl-peroxy- (3-phenyl )propy1idene-2 peroxy] 1,3-diisopropylbenzene, having the following characteristics:

lodometric titration: 75%

Decomposition temperature: 132C Halflifc at 123C: 30 minutes C '70:found 72.971 (calculated 71.44)

H "/1: found 8.57: (calculated EXAMPLE Into a flask provided with astirrer were introduced 50 cc of benzene, 50 cc of ethyl ether, 21.4 gof 1,3- diisopropylbenzene-bis-hydroperoxide (sodium salt) at 67percent, 19.3 g of 4-tert.butyl-cyclohexanone, and 10 g of groundanhydrous calcium chloride. This mixture was then cooled down and over aminute period there were introduced dropwise 20 g of HCl at 36 percent.The mixture was then subjected to stirring for 1 hour at 5C.

The organic solution was washed with water and was then dehydrated withanhydrous sodium sulfate. The residue (32 g determined by analysis),identified as a-a[ 1-hydroxy-(4-tert.-butyl)-cyclohexylidenelperoxy]1,3-diisopropylbenzene, was kept in a solution. An analyticalisolated sample showed the following characteristics:

lodometric titre: 95'71 Decomposition temperature: 78C Half-lifc at 110C 30 minutes C "/1: found 71.371 (calculated 71.87) H 7c found 100%(calculated 10.18)

EXAMPLE l6 Into a flask provided with a stirrer were introduced 32 g ofa-a'[ l-hydroxy-(4-tert.-butyl)cyclohexylidene- 1 peroxy]1,3-diisopropylbenzene, dissolved in 50 cc of benzene and 50 cc ofether, and 15 g of anhydrous calcium chloride. Over a period of 20minutes there were then introduced into the mixture, at a temperatureof15C, 43.9 g of cumene hydroperoxide at 83.4 percent. The solution wascooled down again to -15C, and there were introduced 10 g of HCl at 36percent over a 10 minute period. The exotherm caused the temperature torise to 5C and the solution was then left under stirring for one hour atbetween 5 and 0C. The organic phase was washed with water, with NaOH at5 percent, and then again with water until reaching neutrality. Thesolvent was then removed under vacuum at 50C, thereby obtaining aslightly oily residue, identified as an a-a'[l cumyl-peroxy(tert.-butyl)cyclohexylidene-l peroxy]1,3-diisopropylbenzene, and it showed thefollowing characteristics:

lodometric titre: Decomposition temperature: 1 14C Half-life at 125C: 30minutes C "/0: found 75.1% (calculated 74.4) H "/1: found 8.5%(calculated 8.52)

EXAMPLE 17 200 cc of n-hexane, 50 g of 1,3-diisopropylbenzenebis-hydroperoxide-sodium salt at 60 percent, 29 g of acetoacetic acidethyl ester at 99 percent and 30 g of ground anhydrous calcium chloridewere introduced into a flask provided with a stirrer. The mixture wasthen cooled down to l 05C and over a period of 30 minutes there wereintroduced 45 g of HCl at 36 percent. The mixture was then left understirring for 1 hour at 5C. The organic phase was then washed with waterand thereafter was dehydrated with anhydrous sodium sulfate. Thea-a[2-hydroxy-( 3 ethoxy-carbonyl)-isopropylidene-2 peroxy]1,3-diisopropylbenzene thus obtained (43 g determined analytically)showed the following characteristics:

lodometric titre Decomposition temperature 47C Half-life at 1 18C 30minutes C found 60.1 (calculated 59.24) H 72: found 7.65 (calculated7.87)

EXAMPLE 18 Into a flask fitted with a stirrer were introduced 43 g ofct-a [2-hydroxy-(3 dene-2 peroxy] 1,3-diisopropylbenzene (obtainedaccording to example 17) dissolved in 200 cc of n-hexane, 40 g oftert.-butyl hydroperoxide at 75 percent and 40 g of ground anhydrouscalcium chloride. The solution was cooled down to 10C and over a 10minute period there were'introduced 30 g of HCl at 36 percent. Thetemperature was allowed to rise to 0C, and the solution was stirred for1 hour at this temperature. The organic phase wasthen washed with water,then with NaOH at 5 percent and then again with water. The

solvent was removed under vacuum care being taken not to exceed 30C,thereby obtaining 47 g of slightly yellow-coloured viscous residueidentified as a-a'[2- tert.-butyl-peroxy-(3 ethoxy-carbonyl)isopropylidene- 2 peroxy] 1,3-diisopropylbenzene. This product showedthe following characteristics:

n,," 1.489 lodometric titre 9771 Decomposition temperature 109CHalf-life at 1 18C 30 minutes C 7:: found 61.4 (calculated 60.93) H /r:found 8.63 (calculated 8.63)

ethoxy-carbonyl )-isopropyli- I (cu coo o c a a 06 CH l $00 0 i a 3EXAMPLE l9 EXAMPLE 21 Into a flask provided with a stirrer wereintroduced VULCANlZATlON cc of 9 g of dlsopmPylbenzem? 5 vulcanizationtests were carried out on mixes of an bis-hydroperoxide at 97,3 percent,18 g of acetoacetic ethylene propylene copolymer having a molar ratioacld. ethyleste.r at 99 pe.rcent and 10 g of anhydrousethylene/propylene 50/50 and a viscosity Mooney ML calcium chloride. Themixture was then cooled down to (1 4) 100C=3i In Table 1 there werecompared C and over a 5 mmu-te period thge were mtro' the vulcanizationrates determined on the same mixes, duced 12 g of HCl at 36 percent. Themixture was then Containing as peroxides respectively: stirred at thistemperature for 1 hour. The benzene a a,(146ft butyl pemxycyclopemylidene l peroxy) phase was washed with water and then treatedwith 1 3 diisopropylbenzene. anhydrous Sulfate? The walm'hydroxyjw a-a(l-tert.-butyl-peroxy-4-tert.-butyl-cyclohexyliethoxycarbonyl)rsopropyhdene-Z peroxy] 1,4 dnsod en e 1 perQxy l4 diisopmpylbenzene;propylbenzene thus obtained (29 g analltlcallydeterwe1t6rtfbutyhpemxwcyclohexylidene I peroxy) mined) showed thefollowing characteristics: 15 1 3 diisopmpyl'benzene.

a-a' [2-ter.-butyl peroxy (3-ethoxycarbonyl) isolodometric titre 97%Decomposition temperature 45C propylidene 2 peroxy] 1,3dnsopropylbenzene, Half-life at 115C 30 minutes c :4: found 58.6(calculated 59.24) dicumylperoxide. H mun! (calculated 7'87) Thevulcanization rate was determined at 177C on a Monsanto TM-lO rheometer.The mixes used in the EXAMPLE 20 test wereof the following composition:

Cc of benzene containing g of a'a'[2'hydrOXy ethylene-propylenecopolymer I00 parts (3-ethoxycarbonyl) rsopropylidene-Z-peroxy1-l,4carbon black 50 parts diisopropylbenzene (obtained according to examplein? l9) and 15 g of anhydrous calcium chloride were introperoxide 001mol duced into a flask fitted with a stirrer. Over a 20 minute period toC i were Introduced g of Table 2 reports the physical characteristics ofvulca- Cumyl hydroperoxlde at percent The lemperatilre nized productsobtained by using a peroxides, respecwas maintained to l5C and over a 10minute period tively, there were introduced 10 g of HCl at 36 percent.Due to the exotherm the temperature rose to 5 C and at a a,(1 tefirbutylperoxy cyclopemylidene 1 peroxy) this temperature the solution was thenleft under stirr f h h h h d 1,3-dnsopropylbenzene, I P or 1 h Orgamc pass was t en was a-a'( ltert.-butyl-peroxy-4-tert.butyl-cyclohexyliwithwater, then with NaOH at 5 percent and again dene l peroxy) 1 4diisopropylbenzene. with water until neutgality. The solvent was removedwe146rt butyl peroxy cyclbhexmdene 1 peroxy) under vacuum at 30 Cthereby obtaining 3 g of a 1 3 diisopropylbenzene. slightly oilystraw-colored residue identified as a-a'[2- 40 cumyl'peroxy 3'ethoxycarbonyl) .lsOprOpyhdemFQ for vulcanization times comprised between 5and 60 peroxy] dnsopropylbenzene havmg the followmg minutes at 150C, incomparison with the physical Charactensncs: properties of the vulcanizedproducts obtained by using dicumyl peroxide and operating at 1653C for avulcanii'fig 3 zation time of 30 minutes (these being the optimalDecomposition temperature 121C Conditions for said p Hu lf lifc a: 122C=30 minutes From the results reported in Table 2, it is quite evig 2 g222% dent that. at low temperatures high vulcanization rates and betterphysical characteristics of the vulcanized product are obtained with theperoxides of the inven' tion as contrasted to the use of dicumylperoxide.

TABLE 1 i vulcanization Rate Peroxide vulcanization at the RHEOMETERTYPE Parts per g of vulcanization vulcanization ethylene/propylenetemperature time copolymer minutes g moles CH3 CH3 TABLE l-continuedvulcanization Rule Peroxide vulcanization at the RHEOMETER TYPE Partsper 100 g of vulcanization vulcanization ethylene/propylene temperaturetime copolymer C minutes g moles cu i": I 3

cu (cn l coo cog-4500 ooc( 3 3 619 H 45 cu cu ca 3 ca 3 CH CH I II II(CK coo c -coo 00((CH 5.66 6

CH CH a-a'l 2-lcr.-hutylper0xy( 3-ethoxycurhonyl) isopropylidcne-Zperoxy]l,3 diisopropylben 6.3 7 zone Dicumylpcroxidc 2.70 14 TABLE 2Physical Characteristics of the Vulcanized Product Peroxidevulcanization Parts per 100 g of Temperature Time ethylene/propyleneminutes co olymer moles g I50 C CH i a (cu coo ooc -coo ooc(c|-1 0,0l5,38 l5 3 3 3 3 CH CH 60 CH CH l a I 3 I 5 (cu coo ooc coO oocuzn 6.7910 a a I a 3 H '5 CH CH 30 cu -c-cl l cu e-CH c cu a a s l c- -coo 0,015,66 (cu coo 00 I 00004 I, 5 CH3 CH '1 30 60 Dicumylperoxide 0,0] 2,7030 TABLE 2 -continued Physical properties of the vulcanized productTensile Elongation odulus Modulus Modulus I.R.H.D. strength at break, at100% at 200% at 300%- hardness kg/cm kg/cm kg/cm kglcm I92 1 SH) 23 509| 6566 I98 470 25 55 I08 66 I87 410 22 54 I04 67 I98 420 23 6I I I9 67I86 380 25 68 I30 67 I 350 78 I55 9 68-69 203 340 27 8I I64 69 202 35026 75 I58 69 I90 330 28 84 I68 69 I78 340 25 72 I48 v 69 I99 490 22 54I03 66 I95 460 23 53 I04 67 203 440 24 56 I I0 67-68 202 4l0 25 63 I2668 I88 400 24 57 I23 68 I80 4l0 2] 58 I I9 68 EXAMPLE 22ylidene-l-peroxy) l,4 diisopropylbenzene, and the On a mix having thefollowing composition:

ethylene/propylene copolymer I00 parts carbon black 50 parts ZnO 3 partssulfur 0,32 parts a-a'l2tcrt. butyl peroxy (3-ethoxycarbonyl)isopropylidene-Z peroxy] I ,3 diisopropylhenzene 0,0] mol was carriedout the vulcanization test at, 150C for 15 minutes. The vulcanizedproduct showed the following physical characteristics:

Tensile strength (kg/cm I85 Elongation at break 412 Modulus at 200%(kg/cm 6| Modulus at 300% (kglcm I08 I.R.H.D. hardness 67-68 EXAMPLE 23Crosslinking The crosslinking tests were carried out on mixessubstantially consisting of low-density polyethylene and peroxide.

In Table 3 there are recorded the physical characteristics ofpolyethylene crosslinked using the peroxides according to the invention,that is, a-a'( l-tert.-butylperoxy-cyclopentylidenl -peroxy) 1,3-diisopropylbenzene, a-a'(1-tert.butyl-peroxy-4-tert.-butyl-cyclohexknown peroxide(dicumylperoxide).

EXAMPLE 24 wherein:

a weight of the test sample after 2l hours at C in xylene, b weight ofthe test sample before the test, c weight of the test sample afterdrying at the end of the test.

density of polyethylene at 80C density of xylene at 80C The obtainedresults, compared with those in which dicumylperoxide was used, arelisted in Table 4.

TABLE 3 Crosslinking of low-density (0. 9l8). polyethylene Physicalcharacteristics,

Moles of I peroxide Crosslinking Yield Tensile Elonga- PEROXIDE in I00gTime Temper. point strength tion 3 of polyminutes C kglcm? Kg/cm' atbreak ethylene None 20 57,8 73

TABLE 3-continued Crosslinking of low-density ((1.918) polyethylenePhysical characteristics.

PEROXIDE Moles of peroxide Yield Tensile Elongastrength tionCrosslinking in 100g Time Temper. point Dicumylpe roxidc of poly minutes"C kg/cm Kg/cm at break ethylene I l (CH C00 006 -COO OOClCH l CH CH 1":i" tcu l coo ooc-Ocoo comm CH CH CH -t I-CH (H -$42M CH CH3Dicumylperoxidc 0,01 20 145 52.9 132 436 TABLE 4 Crosslinking oflow-density (0.918) polyethylene I Degree of swelling.

Moles of peroxide PEROXIDF. in 100g Crosslinking of poly- TimeTemperature Degree of ethylene minutes "C swelling CIH3 :IH3 -.c ((11coo 00C 0O count 0.01 20 145 16,5

Ci" in lcu l coo oof-Qcoo comm CH CH 0.01 20 145 20,2

ci i -C am cu e-CH Variations can, of course, be made without departing60 from the spirit and scope of the invention.

Having thus described our invention, what we desire to secure by LettersPatent and hereby claim is:

l. A tetraperoxide selected from the group consisting of 2-peroxy) 1.3diisopropylbenzene;

l. a-a (2-tert.-butyl-peroxy-2-phenyl ethyl-Z-idene- 65 Z-peroxy] 1,3diisopropylbenzene.

zgz g g UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,92 6 Dated December 23, 1975 Inventor) EGEO SACRINI AND CLAUDIOCAVALLOTTI Page 1 of 5 It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Title page, right side, the formula:

' H QR T H h R,-oo- OO-X-OOCR= S CU R l read R|-00-(|JOOXOO-(]J-00R|Column 3, line 32: "ob-on (4-hydroxy-2,6,8 trimethylnonylidene-4-peroxy) should read o) oL-oL' (4-hydroxy- 2, 6,8 trimethylnonylidene-4-peroxy) Column 5, line 45: "solubility to" should readsolubility in G Column 9, line 9: '(calculated 9.7) should read(calculated 9.79)

I Column 10, line 43: "found 0.2" should read found Q 70.2

Column 11, line 24: "1,4988" should read 1.4988 lines 28-29: "8.5%(calculated 8.52) should read 8.57., (calculated 8.52)

[- Column 12, line 13: "1,4985" should read 1.4985 J zg ggg UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,928,4 4Dated December 23, 1975 t fls) O SACRINI and CLAUDIO CAVALLOTTI Page 2of 5 It is certified that error appears in the aboveidentified patentand that said Letters Patent are hereby corrected as shown below:

I" m Column 13, line 5: "97,3 percent" should read 97.3 percent line 31:"83,4 percent" should read 7 83.4 percent line 39: "3 g" should read 38g line 45: "1,521" should read 1.521

Column 14, line 31: "using a peroxides, should read using as peroxides,

0 Columns 15-16, column 1 of Table 1, first formula:

H (H c ShOUld' E": i":

lcu i coo cog-2021 oocrcn l read KNHJCOCQOOEIIQEZQQDOCHNJH Q 3 36 I (Mg-CH CH -CH (NJ-(4H: ca -:01 0,

Columns 15-16, column 1 of Table l: G-OL'[2-ter.-butylperoxy(3-ethoxycarbonyl) isopropylidene-Z peroxy]l,3diisopropylbenzone" should read OL-OL' [2-ter.-buty1-peroxy(3ethoxycarbonyl) isopropylidene-Z peroxy]1,3

diisopropylbenzene Columns 15-16, column 2 of Table 2: "0,01" shouldread 0.01 Q

Columns 15-16, column 3 of Table 2: "5,38" should read 5.38

Patent No.

Inventor) EGEO SACRINI and CLAUDIO CAVALLOTTI UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION 928,464 Dated December 23, 1975 Page 5of 5 It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Column l7, line 30: "0,32" should read 0.32 line 33:

I Columns Columns Columns H52, 7" 52,9

Columns read Columns Columns "16,5" 20, 2 21,3

[SEAL] "0,01" should read 0.01

17-18, column 5 of Table 3: "57,8" should read 19-20, column 2 of Table3: "0,01" should read 19-20, column 5 of Table 3:

19-20, column 2 of Table 4: "0,01" should read 19-20, last column ofTable 4:

should read 16.5

Signed and Scaled this Twenty-eighth Day Of September 1976 Arrest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN ('ummissl'mwr qflalenlxand Trademarks

1. A TETRAPEROXIDE SELECTED FROM THE GROUP CONSISTING OF
 1. A-A''(2-TERT.-BUTYL-PEROXY-2-PHENYL ETHYL-2-IDENE-2 PEROXY 1,3DIISOPROPYLBENZENE;
 2. A-A'' (2-TERT. -BUTYL-PEROXY-2-PHENYLETHYL-2-IDENE-2PEROXY) 1,4 DIISOPROPYLBENZENE;
 2. Alpha - Alpha ''(2-tert.-butyl-peroxy-2-phenyl ethyl-2-idene-2-peroxy) 1,4diisopropylbenzene;
 3. Alpha - Alpha '' (2-cumyl peroxy-2-phenylethyl-2-idene-2-peroxy) 1,3 diisopropylbenzene;
 3. A-A'' (2-CUMYLPEROXY-2-PHENYL ETHYL-2-IDENE-2-PEROXY) 1,3 DIISOPROPYLBENZENE;
 4. A-A''(2-CUMYL PEROXY-2-PHENYL ETHYL-2-IDENE-2-PEROXY) 1,4 DIISOPROPYLBENZENE;4. Alpha - Alpha '' (2-cumyl peroxy-2-phenyl ethyl-2-idene-2-peroxy) 1,4diisopropylbenzene;
 5. Alpha - Alpha '' (2-tert.-butyl peroxy-(3 phenyl)propylidene-2-peroxy) 1,3 diisopropylbenzene.
 5. A-A'' (2-TERT-BUTYLPEROXY-(3 PHENYL) PROPYLIDENE-2PEROXY) 1,3 DIISOPROPYLBENZENE.